Ecotoxicology and Environmental Safety 145 (2017) 57–68

Contents lists available at ScienceDirect

Ecotoxicology and Environmental Safety

journal homepage: www.elsevier.com/locate/ecoenv

Green synthesis of graphene from recycled PET bottle wastes for use in the MARK
adsorption of dyes in aqueous solution
⁎
Noha A. El Essawya, , Safa M. Alib, Hassan A. Faragc, Abdelaziz H. Konsowac,
⁎
Mohamed Elnoubyd, Hesham A. Hamade, ,1
a
Advanced Technology and New Materials Research Institute (ATNMRI), City for Scientific Research and Technological Applications (SRTA-City), New Borg El-Arab City,
21934 Alexandria, Egypt
b
Nucleic Acid Research Department, Genetic Engineering and Biotechnology Research Institute (GEBRI), City for Scientific Research and Technological Applications
(SRTA, City), New Borg El-Arab, 21934 Alexandria, Egypt
c
Chemical Engineering Department, Faculty of Engineering - Alexandria University, Alexandria 21544, Egypt
d
Nanomaterials and Composites Research Department, Advanced Technology and New Materials Research Institute (ATNMRI), City for Scientific Research and
Technological Applications (SRTA-City), New Borg El-Arab City, 21934, Alexandria, Egypt
e
Fabrication Technology Research Department, Advanced Technology and New Materials Research Institute (ATNMRI), City for Scientific Research and Technological
Applications (SRTA-City), New Borg El-Arab City, 21934, Alexandria, Egypt

A R T I C L E I N F O A B S T R A C T

Keywords: Polyethyleneterephthalate (PET) is an important component of post-consumer plastic waste. This study focuses
PET on the potential of utilizing "waste-treats-waste" by synthesis of graphene using PET bottle waste as a source
Waste management material. The synthesized graphene is characterized by SEM, TEM, BET, Raman, TGA, and FT-IR. The adsorption
Graphene of methylene blue (MB) and acid blue 25 (AB25) by graphene is studied and parameters such as contact time,
Adsorption
adsorbent dosage were optimized. The Response Surface Methodology (RSM) is applied to investigate the effect
Cationic dye
Anionic dye
of three variables (dye concentration, time and temperature) and their interaction on the removal efficiency.
Adsorption kinetics and isotherm are followed a pseudo-second-order model and Langmuir and Freundlich
isotherm models, respectively. Thermodynamic parameters demonstrated that adsorption of dye is spontaneous
and endothermic in nature. The plastic waste can be used after transformation into valuable carbon-based na-
nomaterials for use in the adsorption of organic contaminants from aqueous solution.

1. Introduction returned to the valuable application of PET as a waste is limited because

Over the last decades, made-up polymers have become a sophisti-
cated part of our community. Polyethylene terephthalate (PET) is one of
the most common, abundant industrial and municipal wastes. It is re-
lated to the thermoplastic polyester that enormous consumed markedly
in the last few years in pharmaceutical, food and soft drink bottles and
containers industries due to its excellent properties such as; high
thermal stability, transparency, low cost, easy to handle, flexibility in
design, inertness towards food, negligible permeability to CO2 and
malleability resistance to both weak and strong mineral acids, oxidizing
agents, sunlight and microorganisms (Association of Plastic
Manufacturers in Europe, 2001; Parra et al., 2004).
Although the significant fastest expansion rate in the plastic residue
production, it led to severe an environmental issue. PET is considered is
one of the most abundant municipal and industrial wastes that may be
unsuitable mechanical properties, thermal stability as well as the low of
electrical conductivity (Dutt and Soni, 2013; Mallakpour and
Behranvand, 2016). Therefore, the disposal of this waste represents a
major challenge for all over the world, especially in developing coun-
tries for waste and environmental management. The most popular ap-
proach to eliminate the PET waste is by means of incineration with
energy recovery, chemical recycling or feedstock recycling to produce
gaseous and liquid products and carbon-enriched materials (Mishra
et al., 2003). For several years, incineration in landfill sites has been a
common practice in the handling process of PET residues. However, this
method may also negatively affect the environment as it carries out
with air consumption and the release of heat and volatile compounds
(Saha and Ghoshal, 2005). Another alternative would be the use of the
spare PET bottles as an excellent candidate to be used a promising
precursor in the synthesis of carbon-based materials as, for instance,

⁎
Corresponding authors.
E-mail addresses: nony_essawy@yahoo.com (N.A. El Essawy), heshamaterials@hotmail.com (H.A. Hamad).
1
Present address: Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Granada, 18071 Granada, Spain.

http://dx.doi.org/10.1016/j.ecoenv.2017.07.014
Received 5 April 2017; Received in revised form 4 July 2017; Accepted 5 July 2017
Available online 11 July 2017
0147-6513/ © 2017 Elsevier Inc. All rights reserved.
N.A. El Essawy et al.
carbon microspheres, carbon nanotubes (Bazargan and McKay, 2012)
or activated carbons (Mendoza-Carrasco et al., 2016) due to it has a
high content of carbon and negligible amounts of mineral impurities in
its chemical constitution. (Nakagawa et al., 2004).
In order to promote a more competitive carbon material, it is vital to
consider developing carbon based materials from the renewable re-
sources as waste polymers and agriculture waste (El Essawy et al.,
2016; Deng et al., 2016). The main motivation of utilizing these sources
is to provide “green and sustainable” alternatives with low-cost raw
materials for large scale production of clean carbon based structures.
An assortment of dyes is used extensively in many industries, such
as dyeing, printing, paper and pulp, textiles, plastics, leather, cosmetics,
and food industries. Many of the dyes and their products are harmful
and pose severe environmental problems. Dyes usually have complex
aromatic molecular structures which make them more stable, resistant
to fading, difficult to bio-degradation and inhibit sunlight penetration
into the stream which is affecting the aquatic ecosystem. Moreover,
they are toxic to some microorganisms and may cause destruction of
their catalytic capabilities (Forgacs et al., 2004). Thus, treating the
effluents of these industries before they are released into the water
system is a must.
Various techniques have been used to treat dye-polluted water, in-
cluding chemical precipitation, ion exchange (Sheng et al., 2016a, b, c;
Elkady et al., 2014, 2016), membrane filtration (Ciardelli et al., 2001),
adsorption (Sheng et al., 2016a, b, c; Abd Elhafez et al., 2017), TiO2-
photo-catalytic degradation (Hamad et al., 2015a, 2015b, 2016; Fathy
et al., 2016), solid-phase extraction (Wu et al., 2015a), microbiological
decomposition and electrochemical technologies (Bassyouni et al.,
2017). However, many synthetic dyes are chemically stable and re-
sistant to photodegradation and biodegradation (Forgacs et al., 2004;
Rafatullah et al., 2010). Most of dye removal methods have some lim-
itations such as high capital investment and operation costs.
Adsorption is found to be an alternative technique for removing
dyes from wastewater (Yu et al., 2014; Idris et al., 2011; Sivukumar and
Palanisamy, 2009). In fact, a chemical or physical bonding retains the
atoms, molecules, or ions on the surfaces of solids. A number of ad-
sorbents have been used for the removal of dyes from polluted water;
such as activated carbon (Nasuha and Hameed, 2011), carbon nano-
tubes (Yu et al., 2014; Wu et al., 2015b), graphene (Kui et al., 2012; Yu
et al., 2015, 2016a), graphene oxide nanosheet (Yu et al., 2016b), re-
duced graphene oxide and its magnetic composite (Jin et al., 2015);
nano zerovalent iron (Hu et al., 2016) and immobilized on carbon na-
notubes (Sheng et al., 2016a, b, c). Therefore, the development of new
effective, low-cost and eco-friendly adsorbent with high efficiency for
dye removal from the water system is attracting the increased attention
of the researchers worldwide.
Therefore, the aim of the present novel work is to prepare graphene
from PET bottle waste by simple, reproducible and affordable method
which involves the thermal decomposition of PET waste in a closed
system under autogenic pressure. The adsorption behavior of the pre-
pared graphene is evaluated for cationic and anionic dye removal.
Methylene Blue (MB) is selected as a model for basic dye (cationic dye)
and Acid Blue 25 (AB25) as a model for acidic dye (anionic dye). The
effects of important factors including, initial dye concentration, time,
temperature and solution pH are examined as input variables on the dye
removal efficiency through the Response Surface Methodology (RSM)
as a powerful statistical technique which has shown a growing interest
among different researchers worldwide (Rahimdokht et al., 2016). In
addition, the kinetics, equilibrium, and thermodynamics studies of the
adsorption process have been discussed. Wastes-treats –wastes are a
demanding area as it has double benefits which are water treatment and
waste management.
58
Ecotoxicology and Environmental Safety 145 (2017) 57–68
2. Materials and experimental procedure
2.1. Starting materials and reactants
Mineral water bottles waste (Baraka-Nestle bottled water company
in Egypt) as a source for PET were used in the present study. All the
reagents used were commercially available and used without further
purification. Acid blue 25 (AB25) and methylene blue (MB) were ob-
tained from Sigma-Aldrich (USA). Properties and structure of MB and
AB25 dyes were shown in Table S1. All solutions were prepared with
ultra-pure water under ambient conditions.
2.2. Graphene synthesis from PET bottle wastes
First, waste PET bottles were crushed and sieved to obtain the de-
sired size fractions (1–3 mm) using a conventional sieve-shaker. Then
2 g of raw PET waste was introduced into an enclosed 50 mL stainless
steel autoclave reactor (SS316). The closed stainless steel reactor was
placed inside the center of an electric furnace and heated to 800 °C with
a rate of 8 °C min−1 and maintained at this temperature for 1 h. After
that the system was left to cool overnight. The resulted dark products
were collected and crushed. As it was illustrated in Fig. 1, the bottle
wastes were used as a precursor for the synthesis of graphene.
2.3. Characterization of the prepared graphene
The prepared sample was characterized using different physical and
chemical techniques. Scanning electron microscope (SEM) is used to
investigate the surface topography of the prepared sample with JEOL,
model: JSM 6360 LA, Japan. Prior to the investigation, the sample was
coated with gold using sputtering coater (model: S150B, Edwards High
Vacuum Ltd., England) in order to avoid the buildup of local electrical
charges.
Transmission electron microscope (TEM) (TECNAI G20, Super twin,
Double tilt, FEI, Netherland with EDAX) was employed to obtain images
for studying the nanostructure and elemental analysis (qualitative and
semi-quantitative analysis) of the prepared sample. In order to prepare
the sample for TEM analysis, approximately 1 mg of the dry black
powder was dispersed in 15 mL of ethanol using an ultrasonicator
and10μl of this dispersion was put on a coated copper grid. The dried
grid was then examined under an electron microscope (HR-TEM, high
resolution transmission electron microscope operating at 200 kV).
Two different modes of imaging were employed; the bright field at
electron accelerating voltage 200 kV using lanthanum hexaboride
(LaB6) electron source gun and diffraction pattern imaging. Eagle CCD
camera with (4k*4k) image resolution was used to acquire and collect
transmitted electron images. TEM Imaging and Analysis (TIA) software
was used for spectrum acquisition and analysis of EDAX peaks.
Crystallographic information about the micro-structure of sample
was obtained from powder X-ray diffraction (XRD) data collected with a
(Schimadzu-7000, U.S.A.) with CuKα radiation beam (λ =
0.154060 nm). The finely powdered sample was packed into a flat
aluminum sample holder, where the X-ray is generated at 30 kV and
Fig. 1. Schematic representation of synthesis of graphene from PET recycle bottles.
N.A. El Essawy et al.
30 mA with a copper target. Scans are performed at 4°min−1 for 2θ
values between 10 and 80̊.
Thermal characteristics of PET and produced graphene were mea-
sured by TGA-50H, Shimadzu (Japan) with heating rate 10 °C/min
(30 mL/min) up to 800 °C under air atmosphere.
Raman spectroscopy was performed on the dried sample at room
temperature using Senterra Raman spectrometer, Bruker- Germany
with a 514.5 nm excitation wavelength and power output of 10 mW to
determine the extent of graphitic disorder within the prepared material.
Each measurement was taken for 60 s and repeated four times in the
range of wave numbers from 40 to 3500 cm−1.
Fourier transform infrared (FTIR) analysis was applied to determine
the surface functional groups, using a Bruker ALFA FTIR spectrometer
(Bruker Corporation, Ettlingen, Germany), where the spectra were re-
corded from 400 to 4000 cm−1.
Finally, The Brunauer-Emmett-Teller (BET) surface area and total
pore volume were determined using BET and the Barret- Joyner-
Halenda (BJH) adsorption methods.
2.4. Adsorption tests
Stock solutions of MB and AB25 of 500 mg L−1 were prepared by
dissolving 0.5 g of dye in 1 L of ultrapure water. The effects of contact
time, initial dye concentration, adsorbent dose, solution pH, and tem-
perature of the dye adsorption process using the prepared material were
investigated. Desired temperature was controlled by using a tempera-
ture-controlled water bath shaker. All pH measurements were carried
out using a pH meter and solution pH were adjusted using 0.1 M HCl
and 0.1 M NaOH.
At a certain time, the supernatant was taken out and filtered, and
the final dye concentration was determined using UV–Vis spectrometer
at the wavelength of 650 and 600 nm for MB and AB25 dyes, respec-
tively. The following formula was used to determine the adsorbed dye
amounts per gm of the prepared graphene (q) either at equilibrium (qe)
or at specific times (qt):
(C0 − Ce)
qe = V pends on the saturation level of monolayer (Elkady et al., 2015). The
m (1)
(C0 − Ct )
qt = V qe
m (2)
Where; qe and qt (mg g−1) are the amounts of dye adsorbed per unit
weight of the adsorbent at equilibrium and t time, respectively; C0, Ce
and Ct (ppm = mg L−1) are the dye concentrations at initial, equili-
brium and t time, respectively; V (L) is the volume of dye solution; and
m (g) is the weight of the adsorbent.
While dye removal efficiency (R % %) was calculated using the
following equations:
C 0 − Ct
R% = ×100
C0 (3)
2.5. Adsorption procedure by response surface methodology (RSM)
The response surface methodology which was described in the ex-
periment of a Box-Behnken design (Box and Behnken, 1960), used to
determine the optimum conditions for MB and AB25 dye removal using
prepared graphene from waste PET bottles. The design matrix with 13
trials was chosen to evaluate the interaction of different operating
conditions (Pajootan et al., 2014). Box-Behnken design with three
factors at three levels (−1, 0 and 1) was taken into consideration with
regard to the adsorption process and a total number of 13 experimental
runs were conducted to evaluate the effect of three independent vari-
ables (X1: time (min), X2: dye concentration (mg L−1) and X3: tem-
perature (°C)) on the performance of adsorption process. The response
function (dye removal efficiency (%) was further optimized to reach a
59
Ecotoxicology and Environmental Safety 145 (2017) 57–68
desired value by Response Optimizer. Data analysis and optimization
procedure were performed using the statistical software "Statistica".
After the optimization of adsorption process by response optimizer, the
isotherm, kinetic and thermodynamic parameters of MB and AB25 re-
moval were investigated by using prepared carbon nanomaterials.
2.6. Kinetics of adsorption process
Kinetics study was important as it describes the uptake rate of ad-
sorbate. The rate and mechanism of the dye adsorption process onto
adsorbent could be elucidated based on kinetic studies. In order to
elucidate the adsorption kinetics, the pseudo-first-order and pseudo-
second-order models were applied.
qt = q e [1– exp (−k1t)] (4)
k2q 2e t
qt =
1+k2q e t (5)
Where; k1 and k2 are pseudo-first-order and pseudo-second-order ad-
sorption rate constants, respectively.
2.7. Dye sorption isotherms
The dye sorption capacity of the prepared material at different in-
itial concentrations at equilibrium can be illustrated by the adsorption
isotherms. Adsorption isotherms describe how the adsorbate interacts
with adsorbents and give a thorough understanding of the nature of
interaction. Several isotherm equations have been developed and em-
ployed for such analysis and the two important isotherms of Langmuir
and Freundlich isotherms were applied.
2.7.1. Langmuir isotherm model
Langmuir's isotherm was used for monolayer adsorption on a sur-
face containing a finite number of identified sites with negligible in-
teraction between adsorbed molecules and assumes uniform energies of
adsorption on the surface. In addition the maximum adsorption de-
Langmuir isotherm is represented by the following linear equation:
1 C
= + e
Ce KL qm qm (6)
Where; qe is the solid-phase dye concentration in equilibrium with the
liquid-phase concentration Ce expressed in mole L−1, qm is the max-
imum monolayer adsorption capacity (mg g−1), and KL is an equili-
brium constant (L mol−1). A straight line with slope of 1/qm and in-
tercept of 1/qmKL is obtained when Ce/qe is plotted against Ce. The
separation factor (RL) is a dimensionless constant which is an essential
characteristic of the Langmuir model. The equation of RL is expressed
as:
1
RL =
1 +KL C0 (7)
−1
Where Co (mg L ) is the highest studied initial dye concentration, (Co
= 200 mg L−1).
RL indicates if the isotherm is unfavorable when RL > 1, linear at RL
= 1, favorable at 0 < RL < 1, or irreversible at RL = 0 (Elkady et al.,
2016).
2.7.2. Freundlich isotherm model
Adsorbents that follow the Freundlich isotherm equation are as-
sumed to have a heterogeneous surface consisting of sites with different
adsorption potentials (Elkady et al., 2014), and each type of site is as-
sumed to adsorb molecules, as in the Langmuir equation:
1
ln q e = ln Kf + ln Ce
n (8)
N.A. El Essawy et al. Ecotoxicology and Environmental Safety 145 (2017) 57–68

Where; Kf is constant (function of the energy of adsorption and tem-

perature) and n is a constant related to adsorption intensity, by plotting
ln qe versus ln Ce which gave a straight line with slope of 1/n and
intercept of ln KF. The magnitude of the "n" shows an indication of the
favorability of adsorption (Gopinath et al., 2009). In general, if "n" is
greater than 1, that means adsorbate is favorably adsorbed on the ad-
sorbent whereas if "n" is lower than 1, that illustrates the adsorption
process is chemical in nature (Elkady et al., 2016).

2.8. Adsorption thermodynamics

Adsorption thermodynamics experiments were performed at the

optimum condition obtained by RSM for various temperatures (25, 35,
45 and 55 °C). Thermodynamic parameters were calculated by the
following equations where KD is the equilibrium partition constant, ΔG
(kJ mol−1) is the Gibbs free energy change, R (8.314 J mol−1 K−1) is
the universal gas constant, T (K) is the temperature, ΔH (kJ mol−1) is
the enthalpy change and ΔS (kJ mol−1 K−1) is the entropy change.
qe
KD =
Ce (9)

ΔG = −RT ln KD (10)

ΔS ΔH
ln KD = −
R RT (11)
The values of ΔG were calculated from the KD values for each
temperature, the values of ΔH and ΔS were calculated from the slope
and intercept of the plot of ln KD versus 1/T, respectively (Gopinath
et al., 2009; Abd Elhafez et al., 2017).

3. Results and discussion

3.1. Chemical composition of PET

The elemental analysis of PET waste is revealed that this plastic

polymers are as a precursor in the preparation of graphene, especially
due to its high carbon content and absence of inorganic matter and
other impurities in their composition. This is an important property of
this material for the presence of inorganic compounds could exert un-
desirable effects on processes such as adsorption of solutes in solution,
catalysis, etc.

3.2. Characteristics of the prepared graphene

The SEM micrograph of the synthesized graphene is shown in Fig. 2-

a. It exhibits the fiber network morphology with void space in between Fig. 2. (a) SEM image, (b) TEM image, c) EDX analysis of the synthesized graphene.

which can provide access to the porosity. On the other hand, different
sizes that suggest a progressive consumption of material probably due
to the fact that activation affect not only the surface but also the inner
parts of the material. Meanwhile, as illustrated in Fig. 2-b the TEM
image shows the presence of few-layers of graphene as relatively
transparent sheets entangled and rippled with each other, graphite
deposits are also observed. Energy Dispersive X-ray (EDX) is used to
analyze the elemental composition of graphene as shown in Fig. 2-c.
The elemental composition consisted of high amount carbon and traces
of oxygen.
The XRD diagrams of the prepared sample are shown in Fig. 3-a. The
disordered structure is reflected by the broad X-ray diffraction peaks
centered at approximately 26, 42.3 and 44.3 2θ which correspond to
the (002), (100) and (101) reflections, respectively for graphene. It is
typical for highly amorphous graphite like carbons (Zhang et al., 2016;
Sergiienko et al., 2009). The broad (002) peak, in particular, en-
compasses diffuse sets of inter-layer distances which, on average, are
larger than those in crystalline graphite (typically 0.344–0.355 nm).
The presence of the (101) peak suggests a stacking order of graphene
sheets (Shen and Lua, 2013).
Raman spectroscopy is also widely used to analyze carbon materials
and provided information about defects density, disorder structures,
and doping levels. Generally, the Raman spectrum of graphene is
characterized by two main features, the G mode, arising from the first
order scattering of the E2 g phonons of sp2 C atoms (usually observed at
1596 cm−1) and the D mode, which attributed to the vibration of
carbon atoms with dangling bonds for the in-plane terminated dis-
ordered graphite component, (at 1360 cm−1). Fig. 3-b shows the
Raman spectrum of the prepared graphene. The figure is typical for a
hard carbon, with a broad band at 1331–1338 cm−1 representing a
highly disordered (D) graphite arrangement (imperfect structure of
amorphous carbons) and a band at 1573–1599 cm−1, characteristic of a
more ordered graphitic (G) structure. When the bond lengths and an-
gles of graphene are modified by strain, caused by the interaction with
other graphene layers or due to external disorder, the hexagonal sym-
metry of graphene is broken (Malard et al., 2009; Ni et al., 2008). The
G-band is, therefore, highly sensitive to strain effects in sp2 nano-car-
bons and can be used to investigate any modification to the flat geo-
metric structure of graphene, such as the strain induced by external

60
N.A. El Essawy et al.
Fig. 3. a) XRD pattern and b) Raman spectra of the syntheized graphene, and c) TGA of
PET and graphene.
forces, by one graphene layers on another in few layer graphene. The
intensity ratio of the D and G-bands (ID/IG) is quantifying the relative
levels of disordered structure and it is a good indicator of sample
quality (Sergiienko et al., 2009). However, the intensity ratio of the D
and G bands is 1.13 for prepared graphene.
Fig. 3-c depicts the TGA of the PET bottle as a precursor and syn-
thesized graphene. It shows that the degradation process of PET mainly
occurs in one step. The temperature region is from ambient temperature
to 800 °C under air atmosphere. As can be observed, PET showed no
significant weight loss until 350 °C and only 13 wt% weight loss is seen
from 25 to 100 °C which can be related to the loss of physically ad-
sorbed water and the loss of volatile compounds (Hamad et al., 2014).
Generally, PET and synthesized graphene thermally stable up to 360
and 485 °C, respectively. As expected, this sample is totally decomposed
at high temperature (> 500 °C) and the ash content is quite low (about
1.74% and 2.46%) since the PET polymer is essentially composed of
organic matter. The formation of carbon species during the thermal
decomposition of PET may be regarded to a competition between a
61
Ecotoxicology and Environmental Safety 145 (2017) 57–68
Fig. 4. (a) N2 adsorption–desorption isotherms for prepared graphene at 77 K, and (b)
FTIR spectra before and after adsorption of MB and AB25.
chain scission to generate volatile species and a condensation process to
form carbon structure (Yuan et al., 2008). It is much easier for aromatic
polymers to convert into polyhexagonal carbon layers compared with
aliphatic polymers. Subsequently the aromatic (rich in benzene) prop-
erty of PET makes condensation much easier, which leading to the al-
most simultaneous occurrence of chain scission and condensation ra-
ther than the aliphatic polymer (Lian et al., 2011).
The BET surface area of the PET is lower than 2 m2/g and the
synthesized graphene is 721.7 m2/g (Table S2). Pore size is one of the
main specifications for which adsorbents are selected for a particular
application. As shown in Fig. 4-a, the N2 adsorption and desorption at
77 K of graphene increased rapidly at low relative pressure, and at high
relative pressure the adsorption volume stabilized, the shape of ad-
sorption isotherms evolves from an isotherm exhibiting a very closed
knee, which is classified as type I according to IUPAC classification that
indicates the presence of large fractions of micropores (Gao et al.,
2013). Furthermore, the Dap value for graphene is 2.1007 nm as shown
in Supplemental Table S2, which is very near to 2.0 nm indicating a
great development of micropores whereas micropores (< 2 nm) and
mesopores (2–50 nm) are based on the classification adopted by IUPAC
(Gao et al., 2013). The BET surface area, mean pore diameter and total
pore volume values are indicated that the prepared graphene has ap-
propriate properties for the removal of dye molecules from waste water.
3.3. An exploratory adsorption study by FTIR
The existence of several functional groups peaks is estimated before
and after adsorption of MB and AB25 dyes using FTIR that shown in
Fig. 4-b. The graphitization of PET waste by thermal decomposition can
be confirmed due to the presence of IR absorption peak around
1600 cm−1 corresponding to the in plane C˭C vibration, which is an
intrinsic characteristic of sp2 graphitic materials (Hu et al., 2017). As
shown, graphene has four characteristic peaks at 3447, 1636, 1219, and
1105 cm−1, which may be attributed to the stretching vibration of O–H,
N.A. El Essawy et al.
C˭O of carboxyl groups, esters C–O–C ethers or phenol groups, and
alkoxy C–O, respectively (El-Remaily and Hamad, 2015; Adel et al.,
2016; Yu et al., 2016). That is evidenced; the prepared graphene con-
sists of several surface functional groups such as oxygen surface groups
are frequently in graphene which affect positively on the adsorption
ability of organic pollutants in liquid solution.
As shown in Fig. 4-b (the results summarized in Supplementary
Table S3), many significant differences occurred for graphene after
adsorbing MB and AB25 [by mixing 5 mg of prepared graphene with
25 mL of 100 mg L−1 dye solution in a mechanical shaker at a tem-
perature of 25 °C for 30 min and an agitation speed of 200 rpm]. For
instance, there are distinct and significant changes in the adsorption
peak frequencies of OH, C˭C, C˭O and C-O-C suggesting that, such io-
nize the functional groups on the adsorbent surface are able to link and
interact with the dye molecule. Moreover, the mechanism of adsorption
can be deduced by its dependence on such functional groups especially
the hydroxyl group. The changes in the FTIR spectrum are the clue of
the formation of multiple carbon-carbon bond structures as well as the
elimination of oxygen and hydrogen atoms which originally present
(Gao et al., 2013).
3.4. Adsorption studies
The structure of MB and AB25 used in the present study is given in
Table S1. The pKa of the functional groups associated with MB and
AB25 renders them charged depending on the pH used. On the other
hands, AB25 possesses a sulfonic group that imparts negative charge
resulting in the repulsion between graphene and the dye molecule and
hence lower adsorption is observed as compared to MB.
3.4.1. Effect of contact time
As shown in Fig. 5-a the qt value increased rapidly in the beginning,
then increased slowly and finally became constant over a certain time.
This can be due to the fact that, there are free surface sites available for
adsorption at the initial adsorption stage (Yu et al., 2016). At the fur-
ther stages, the remaining unoccupied surface sites are hard to be uti-
lized due to repulsive forces between the dye molecules adsorbed onto
adsorbent and those in the solution. The adsorption of MB dye on
graphene reached equilibrium after 30 min. So, 30 min is chosen to be
the optimum contact time with adsorption capacity 481 mg g−1. While
for AB25 it is evident as per Fig. 5-a, the rates of adsorption are fast up
to 25 min and then gradually increased between 30 to 50 min. Based on
experimental results; there is no significant change in the adsorption
capacity after 50 min for AB25; that may refer to the small number of
vacant sites are available. The maximum percentage of AB25 removal
at the equilibrium time is 90% with adsorption capacity 460 mg g−1.
As shown, the color removal of MB dye is quicker than AB25 on the
graphene surface. This is may be due to the fact that polar functional
groups at the opening of pores adsorb water through hydrogen bonds
while the anionic dye molecules suffer columbic repulsion with oxygen-
containing functional groups (carboxyls, carbonyl etc.) present on
graphene.
3.4.2. Effect of initial dye concentration
It is evident from Fig. 5-b that the adsorption is highly dependent on
initial dye concentration. The percentage dye adsorption drops with
increasing initial dye concentration from 50 to 200 mg L−1 at contact
time equal 30 min for MB and 50 min for AB25 at room temperature.
This may be attributed to the repulsive forces between the dye mole-
cules to the adsorbent surface and the bulk phase. At lower con-
centrations, all dyes concentration present in the adsorption sites can
interact with the surface of graphene because of the ratio of available
binding sites to the initial dye is larger (Ali et al., 2016). However, at
higher initial dye concentration, the ratio is low because the adsorption
site is saturated and it will impede the movement of dye toward the
vacant surface sites on the adsorbent surface (Ali et al., 2016).
62
Ecotoxicology and Environmental Safety 145 (2017) 57–68
3.4.3. Effect of adsorbent dosage
It is indicated from Fig. 5-c that the percentage dye removal is en-
hanced as the adsorbent dose increased. The main reason for this be-
havior may be accounted to the greater availability the number active
sites for dye-surface interactions as a result of increase the surface area,
pore volume and the number of binding sites (Ali et al., 2016; Bangash
and Alam, 2009). Another reason may be attributed that the aggrega-
tion of surface area of graphene that is available for adsorption of dye
and increase the diffusion path length (Abd Elhafez et al., 2017). The
optimum dosage to achieve 96% MB dye removal is recorded as
0.2 mg/mL. While, that value achieved 90% for AB25.
3.4.4. Effect of solution temperature
As shown in Fig. 5-d, the percentage dye removal increases with
increasing solution temperature. This behavior indicates that the dye
adsorption process is an endothermic process that give prediction in the
presence of weak attractive forces between surface of graphene and the
dye molecule that evident adsorption mechanism of MB and AB25 onto
graphene is considered as a mainly chemisorption process (Yu et al.,
2016; Elkady et al., 2016). But the percentage dye removal is almost
unchanged at temperature higher than 35 °C for MB adsorption.
Therefore, 35 °C is chosen as the best temperature of the adsorption
process using the prepared material. The adsorption capacity of AB25
increased significantly with the increasing temperature indicating that
the AB25 dye adsorption at higher temperatures is favored.
Generally, these results may be attributed to the rise of solution
temperature, which accelerates the rate of diffusion of dye molecules
from the solution bulk to the adsorbent surface across the external
boundary layer and in the internal pores of the adsorbent. Also, the
increasing of temperature facilitates the attraction of dye ions to the
surface of graphene and increase the rate of ion exchange process due to
the activation of graphene adsorbent material at high temperature
(Elkady et al., 2016). However, as the temperature increases, the mo-
bility of dye molecules increased with the creation of new active sites
and the thickness of boundary layer surrounding the adsorbent de-
creased, which in turn decreased the mass transfer resistance of ad-
sorbate in the boundary layer with temperature.
3.4.5. Effect of pH
The initial pH value of the dye solution is one of the most significant
factors influencing on the adsorption capacity because it can influence
the surface charge of the adsorbent as well as the surface binding sites
and the degree of ionization of the dye (Abd Ellatif and Ibrahim, 2009;
Ali et al., 2016; Elkady et al., 2016). Graphene as adsorbent may con-
tain a large number of active sites and the dye ion uptake can be related
to the active sites and also to the chemistry of dye solution. The impact
of solution pH values on the removal of dyes is determined over a pH
range of 2–12.
It is found out that, the removal percentage of MB increased with
increasing the solution pH and the optimum pH value for MB adsorp-
tion is 12 (Fig. 5-e). This phenomenon may be explained by the fact
that, the cationic dye becomes positively charged when it is dissolved in
water. Thus, in acidic medium the positively charged surface of gra-
phene hinders the adsorption of the cationic MB (Han et al., 2014). As a
result, when the pH of the solution increased, adsorption of MB in-
creased due to an increase in the electrostatic attraction between the
positive dye molecules and the adsorbent surface which is negatively
charged. However, graphene has a positive charge at low pH values due
to the presence of functional groups containing the remaining oxygen.
Moreover, a low pH value means a relatively high concentration of
protons, which competes strongly with MB cationic molecules for the
adsorption sites on the surface. As a result, the removal of MB dye
decreases at low pH values. On the other hand, as the pH value in-
creases, the surface charge becomes more negative sequentially and the
removal of MB increases.
On the other side, the experiment results showed variations in the
N.A. El Essawy et al. Ecotoxicology and Environmental Safety 145 (2017) 57–68

Fig. 5. Effect of processing parameters variation on MB and AB25 decolorization process onto graphene: (a) effect of contact time [Conditions: C0: 100 mg L−1; dose of adsorbent: 0.2 mg/
mL; at 25ᵒC.] (b) effect of initial dye concentration [at dose of adsorbent: 0.2 mg/mL; at 25ᵒC.]; (c) effect of adsorbent dosage [at C0 = 100 mg L−1; at 25ᵒC.]; (d) effect of dye solution
temperature [at C0 = 100 mg L−1; dose of adsorbent: 0.2 mg/mL]; (e) effect of pH [C0 = 100 mg L−1; dose of adsorbent: 0.2 mg/mL at 25ᵒC.].

AB25% removal at pH values of 2–12. It is noticed that the percentage
removal of AB25 increased from pH 2–6 before it decreased gradually
until pH 12. The maximum percentage removal of AB25 observed at pH
6 is 84%. The high percentage removal of the AB25 solution at acidic
pH may be attributed to the electrostatic interactions between the po-
sitively charged adsorbent and the negatively charged AB25 dye anions
(Hanafiah et al., 2012). Therefore, the attraction between sulfonate
groups and positively charged adsorbent surface can be represented by
the following equations:
RCOOH++ RSO–3 → RCOOH + −
··· O3SR
ROH+ + RSO−3 →ROH+···−O3SR
The positively charged adsorbent is generated due to the hydro-
phobic nature of the adsorbent which tended to adsorb positive hy-
drogen ions on the surface when immersed in water (Ali et al., 2016).
Generally, the positive charge in an acidic medium and the negative
charge in basic medium have become developed on the surface of
adsorbent. Therefore, the adsorbent surface can attract the negatively
charged functional groups located on AB25 dye molecules at lower pH
and hence increases the adsorption capacity and decrease at higher pH.
Hence, anionic dye removal by adsorption increases at low pH and
decreases at high pH.
3.5. Optimization using RSM
The adsorption processes are performed according to Box–Behnken
(12)
design which identified the best levels of the variables as time (min.),
dye concentration (mg L−1) and temperature (°C) as illustrated in
(13)
Supplementary Table S4 for MB and AB25 dyes.
The quadratic model explained the statistical relationship between
the selected variables and the response in terms of coded factors is the
best fitted with the following equations.

63
N.A. El Essawy et al. Ecotoxicology and Environmental Safety 145 (2017) 57–68

Fig. 6. Response surface plots for removal efficiency (%) of MB and AB25 onto graphene: effect of time/initial dye concentration for a)MB and b) AB25 [at dose of adsorbent: 0.2 mg/mL;
at 25ᵒC]; effect of time/temp for c) MB and d)AB25 [at C0 = 100 mg L−1; at dose of adsorbent: 0.2 mg/mL]; effect of temp./initial conc. for e) MB and f) AB25 [at time:50 min; dose of
adsorbent: 0.2 mg/mL].

YMB = 95.98 + 1.01625X1 − 5.53875X2 + 1.0875X3 + 0.5975X12
−3.5425X22 +0.415X32 +0.44X1X2 − 0.3025X1X3 + 1.0925X2X3
(14)
YAB25 = 88.97 + 1.555X1 − 23.95125X2 + 4.02875X3 − 0.12875X12
−17.56125X22 −0.78625X32 +0.67X1X2 − 0.85X1X3 + 2.6175X2X3
(15)
where Y is the response (yield of removal) and X1, X2, and X3 are
contact time, dye concentration, and solution temperature, respec-
tively.
The results of the Box–Behnken design can be presented in 3D
presentations with contours. The 3D surface plots show the type of
interaction between the tested variables which allow obtaining the
optimum conditions (Kousha et al., 2015). These plots of the second-
order polynomial equation with two variables keeping constant and the
other two variables within the determined experimental ranges are
given in Fig. 6. The maximum predicted value is represented by the
surface plots.
Fig. 6(a and b) indicates the simultaneous effect of contact time and
dye concentration on dye removal efficiency for prepared graphene.
The dye removal efficiency decreased with an increase in dye con-
centrations from 50 to 150 mg L−1 and the maximum efficiency was
obtained with 50 mg L−1 initial concentrations for both dyes. Fur-
thermore, the removal efficiencies for MB are between 91% and 99%,
which achieved only after the maximum 30 min process that reveals the

64
N.A. El Essawy et al. Ecotoxicology and Environmental Safety 145 (2017) 57–68

high performance of the prepared graphene at studied conditions. Table 1

While for AB25 the removal efficiencies lie between 70% and 97% and Parameters and determination coefficients of the kinetic models for MB and AB25 dyes
adsorption on prepared graphene.
that carried out after 30 min.
Fig. 6(a, b, c and d) exhibit the effect of contact time, the removal MB Initial concentrations (ppm) AB25 Initial concentrations (ppm)
efficiency increases with an increase in contact time and then remained adsorbed on graphene adsorbed on graphene
approximately constant after 50 min. This observation revealed that in
the beginning, the dye molecules are adsorbed externally and the ad- 50 100 150 200 50 100 150 200

sorption rate increased rapidly. When the external surface became sa- qe,exp (mg 246 468 587 743 232 439 546 718
turated, the dye molecules adsorbed into the porous structure of the /g)*
graphene and finally, at some point in time, reached a constant value Pseudo-
where no more dye is adsorbed from the solution. 1st-
order
The fitted surface plots of dye removal efficiency (%) versus the
qe′cal(mg/ 321 671 968 1297 720 1135 1895 4354
combined effect of initial dye concentration and solution temperature is g)
also shown in Fig. 6(e and f). However, by investigating the combined k1(min−1) 0.167 0.162 0.136 0.109 0.267 0.201 0.191 0.196
2
effect of initial dye concentration and solution temperature on dye re- R 0.998 0.993 0.994 0.983 0.953 0.905 0.901 0.920
Pseudo-
moval efficiency, it was realized that when the initial dye concentration
2nd-
is low, the optimum temperature is obtained at lower degree, probably order
due to the existence of a smaller number of dye molecules in the so- qe,cal(mg/ 241 481 610 687 248 455 561 710
lution to be adsorbed on graphene. But, at highly concentrated solu- g)
tions, the effect of heating is less efficient. k2(min−1) 0.004 0.002 0.0017 0.001 0.004 0.002 0.0018 0.0014
2
R 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999
In this respect, the solver function of the Microsoft Excel tools was
used to estimate the optimal levels of the three components. This op- Note: * equilibrium time for MB removal equal 30 min, while for AB25 removal equal
timal levels were obtained from the maximum point of the polynomial 50 min.
model to achieve 99% removal efficiency for MB were 35 mincontact
time, 71.7 mg L−1 dye concentration at solution temperature 45 °C. numerous sorption sites and mass transfer may be included at the
While 95% dye removal for AB25 obtained at contact time 35 min, dye sorption mechanism. So, the pseudo-first-order reaction kinetic model
concentration of 70.58 mg L−1 and 45 °C of solution temperature. was not adequate to describe MB and AB25 dye sorption on the pre-
Thereby, these results emphasize the necessity and value of an opti- pared graphene.
mization process. The pseudo-second-order kinetic model is dependent on the solute
As illustrated in Table S4 of model validations, the agreement be- amount adsorbed on the surface of adsorbent and the adsorbed amount
tween the obtained and estimated removal efficiency showed that using at equilibrium. The model parameters and the correlation coefficient
response surface method to design the experiments can be considered as (R2) values for different initial concentrations were listed in Table 1 and
an effective choice in the optimization of process parameters besides its Fig. S2. As it can be seen, the R2 values obtained are consistently higher
uses as an experimental design and statistical analysis. than those of the pseudo-first-order. In addition, the qe, calculated va-
lues are in a harmony with the experimental qe values (qe,exp). These
3.6. Kinetic models and adsorption mechanism results indicated that the adsorption perfectly obeys the pseudo-second-
order model, meaning that the controlling rate step is chemisorption.
To understand the adsorption process mechanism, the determina- Moreover, the result showed that the rate of adsorption for both dyes
tion of the efficiency and control the residual time of adsorption pro- depended on the availability of adsorption sites on the surface of gra-
cess, the three kinetic models are used to test the experimental data, the phene as adsorbent material, whereas the dye concentration increased
pseudo-first-order and the pseudo-second-order and intra-particle dif- the k2 values was decreased. This may be due to the higher competition
fusion equations. These models are helpful for the design of the sorption for the adsorption site at a high dye concentration compared to low dye
process and adsorption mechanism of determination the controlling concentration (Chen et al., 2011).
steps, such as mass transport and chemical reaction. Kinetic models are To test the diffusion mechanism of MB and AB25 onto the prepared
tested for the kinetics of MB and AB25 dye sorption processes at various graphene, an intraparticle diffusion model has been used at different
initial concentrations (50, 100,150 and 200 mg L−1) using the prepared initial dye concentrations using the following form:
graphene. The kinetic rate constants are calculated using the conven-
tional rate expressions. qt = kit 0.5+C (17)
The pseudo-first-order kinetic model is more suitable for low con-
centration of solute. It can be written in the following form: Where; ki (mg g−1 min−1/2) intraparticle diffusion rate constant which
is the slope of the straight line of qt versus t1/2 and C is the value of the
ln (q e − qt) = ln q e − k1t (16)
intercept which is a constant reflecting the significance of the boundary
Where qe is the amount of dye adsorbed at saturation per gram of ad- layer or mass transfer effect. As shown in Fig. 7 all the plots have the
sorbent (mg g−1), qt is the amount of dye adsorbed at time t per gram of same general aspect, whereas the diffusion mechanism of the adsorp-
adsorbent (mg g−1), and k1 (min−1) is the rate constant of the pseudo tion processes is generally divided into three steps for each curve from
first-order adsorption. By plotting ln (qe-qt) versus time, the rate con- larger pores to micropores. In the first step, the external surface ad-
stants and qe for MB and AB25 sorption on the prepared graphene can sorption or diffusion in macropores occurred at the outer material
be calculated (Fig. S1). The calculated dye sorption capacities, the re- surfaces which are followed by the second step, which is controlled by
action rate constants, and the linear correlation coefficients R2 values intraparticle diffusion; it is the gradual adsorption step. Lastly, the third
for the different studied dye concentrations were investigated in step is the slowest step which represents the final equilibrium step. As
Table 1. The pseudo first order assumes that the adsorption capacity is listed in Table S5, ki increased with increasing dye concentration, as a
limited by only one process or mechanism acting on one class of ad- result of the fact that multitude dye molecules interacted with active
sorbing sites (Abd Elhafez et al., 2017). Comparing the calculated dye sites on adsorbent which caused high adsorption intensity at a high
sorption capacities with the experimental capacity values, it was rea- initial concentration. For all initial concentrations, ki,1 is larger than
lized that the calculated values from the pseudo-first-order equation ki,2, which indicates that the free path available for diffusion became
were far from their comparative experimental values as well as the smaller and the pore dimensions decreased (Wang et al., 2016). The ki,3

65
N.A. El Essawy et al. Ecotoxicology and Environmental Safety 145 (2017) 57–68

Fig. 7. Intra-particle diffusion kinetic model fit for the adsorption of (a)MB and (b) AB25 onto graphene. [Conditions: dose of adsorbent was 0.2 mg/mL; at 25 °C.].

is significantly lower than the others, which confirmed that the third on energy changes of the adsorption process. The thermodynamic
step is the slowest step. parameters were summarized in Table 3. The negative values of ΔG
showed that both dye adsorbent systems were spontaneous in nature.
Furthermore, the decrease in the values of ΔG with the increasing
3.7. Adsorption isotherms
temperature showed clearly that the adsorption was more spontaneous
at higher temperatures (Wu et al., 2015b). The positive values of ΔH
The analysis of the isotherm data is urgent to develop an equation
indicate an endothermic nature of the process. On the other hand, the
which represents the results used for the design. Adsorption equilibrium
positive values of ΔS indicate an increase in randomness in the solid and
is traditionally evaluated by adsorption isotherms. It is obtained from
solution interface during the adsorption process (Yu et al., 2014).
experimental data using Langmuir and Freundlich adsorption isotherm
However, the positive value of ΔS can demonstrate a result of “solvent-
models at different initial concentrations and two different tempera-
replacement” phenomenon, where the dye molecules need to replace
tures (25 °C and 55 °C). According to the correlation coefficients and
the water molecules on the adsorbent surface in order to be adsorbed
parameter values which summarized in Table 2, the R2 of Langmuir
(Kooh et al., 2016; Zhao et al., 2016).
model was very close to 1 and larger than Freundlich model which
suggests that the adsorption was a process which occurred in a homo-
geneous surface. Thus, with the consideration of R2 and the error
4. Conclusions
functions, it was concluded that the Langmuir model best represented
the adsorption data. In addition, the values of RL at low temperatures
This study involved the preparation of graphene via thermal dis-
were higher than those at high temperatures as shown in Fig S3. It can
sociation of Poly-ethylene-terephtalate waste. The results revealed that
be deduced that the adsorption behavior was more effective at high
the prepared graphene has a relatively high surface area and micropore
temperatures (Gao et al., 2013) and the adsorption process was more
volumes and it was found out to be a promising adsorbent for dye re-
irreversible. From Freundlich model, the values of 1/nF which are a
moval from aqueous solutions.
measure of adsorption intensity or surface heterogeneity fluctuate be-
The adsorption efficiency of MB and AB25 is increased with in-
tween 0 and 1 and that elucidate more heterogeneity as the values get
creasing the solution temperature and dose of adsorbent and decrease
closer to zero. Table 2 shows the values of 1/nF at different con-
with increasing initial dye concentration. While the amount of dye
centrations at temperature 25 and 55 °C. It can be seen that all the
adsorbed was increased with increasing contact time at all initial dye
values of 1/n are smaller than 1. However, the results also indicate that
concentrations. Furthermore, the adsorption processes reached equili-
adsorption of both dyes is effective using Freundlich isotherm model.
brium within 30 and 50 min for MB and AB25 respectively which re-
present short time duration. The adsorption of MB was favored at al-
3.8. Adsorption thermodynamics kaline medium and the optimum pH value was found to be 12, while
AB25 adsorption was favored at acidic medium. Whereas, RSM opti-
The adsorption thermodynamics provided some useful information mization results indicated that solution temperature, and dye con-
centrations are the most important variables in the removal of MB and
Table 2 AB25 dyes. In kinetic study, the pseudo-second order kinetic model was
Adsorption isotherm parameters for the adsorption of MB and AB25 dyes onto prepared
found to be well suited for the entire adsorption process of MB and
graphene at adsorbent dosage 0.2 mg/mL.
AB25. Adsorption kinetic was generally controlled by different me-
MB adsorption onto AB25 adsorption onto graphene chanisms, of which the most limiting are the diffusion mechanisms,
graphene including film diffusion and intra-particle diffusion. All equilibrium
data obtained at different temperatures fit perfectly with Langmuir and
Temperature °C 25 °C 55 °C 25 °C 55 °C
Freundlich isotherm models. The negative values of ΔG and positive
Langmuir isotherm values of ΔH and ΔS indicate that the dyes adsorption process is
qm (mg/g) 761.3 867.2 642.9 641.4 spontaneous, endothermic and an increase in randomness occurs at the
kL(L/mg) 0.284 0.782 0.247 1.364 solid or solution interface. The overall results showed that the prepared
R2 0.996 0.999 0.995 0.999
graphene from thermal dissociation of PET waste bottles is an effective
RL 0.014 0.010 0.019 0.005
Freundlich isotherm and low-cost adsorbent for the removal of MB and AB25 from aqueous
KF(mg/g) 183.745 245.145 200.463 368.353 solutions.
1/nF 0.335 0.338 0.317 0.204
R2 0.996 0.976 0.992 0.998

66
N.A. El Essawy et al. Ecotoxicology and Environmental Safety 145 (2017) 57–68

Table 3
Thermodynamics parameters of prepared graphene on the removal of 100 ppm of MB and AB25 at temperature ranged from 25 to 55 °C.

MB adsorption onto graphene AB25 adsorption onto graphene

Temperature °C 25 °C 35 °C 45 °C 55 °C 25 °C 35 °C 45 °C 55 °C

ΔG(kJ/mole) −11.3 −12.1 −13.6 −14.8 −9.8 −10.4 −11.8 −12.6

ΔH(kJ/mole) 18.9 17.6
ΔS(J/mole K) 45.8 38.7

Appendix A. Supplementary material Synthesis and characterization of core–shell–shell magnetic (CoFe2O4–SiO2–TiO2)

nanocomposites and TiO2 nanoparticles for the evaluation of photocatalytic activity
under UV and visible irradiation. New J. Chem. 39 (4), 3116–3128.
Supplementary data associated with this article can be found in the Hamad, H., Abd El-latif, M., Kashyout, A., Sadik, W., Feteha, M., 2015b. Optimizing the
online version at http://dx.doi.org/10.1016/j.ecoenv.2017.07.014. preparation parameters of mesoporous nanocrystalline titania and its photocatalytic
activity in water: physical properties and growth mechanisms. Process Saf. Environ.
Prot. 98, 390–398.
References Hamad, H.A., Sadik, W.A., Abd El-latif, M.M., Kashyout, A.B., Feteha, M.Y., 2016.
Photocatalytic parameters and kinetic study for degradation of dichlorophenol-in-
dophenol (DCPIP) dye using highly active mesoporous TiO2 nanoparticles. J.
Abd Elhafez, S.E., Hamad, H.A., Zaatout, A.A., Malash, G.F., 2017. Management of
Environ. Sci. 43, 26–39.
agricultural waste for removal of heavy metals from aqueous solution: adsorption
Han, Z., Zhu, Z., Wu, D., Wu, J., Liu, Y., 2014. Adsorption kinetics and thermodynamics of
behaviors, adsorption mechanisms, environmental protection and techno-economic
acid blue 25 and methylene blue dye solutions on natural sepiolite. Synth. React.
analysis. Environ. Sci. Poll. Res. 24, 1397–1415.
Inorg., Met. -Org., Nano-Met. Chem. 44, 140–147.
Abd Ellatif, M.M., Ibrahim, A.M., 2009. Adsorption, kinetic and equilibrium studies on
Hanafiah, M.A., Ngah, W.S., Zolkafly, S.H., Teong, L.C., Abdul Majid, Z.A., 2012. Acid
removal of basic dye from aqueous solutions using hydrolyzed oak sawdust. Desalin.
Blue 25 adsorption on base treated Shorea dasyphylla sawdust: kinetic, isotherm,
Water Treat. 6, 252–268.
thermodynamic and spectroscopic analysis. J. Environ. Sci. 24, 261–268.
Adel, M., Mohamed, M.A.A., El-Maghraby, A., El-Shazly, O., El-Wahidy, E.F., 2016.
Hu, B., Huang, C., Li, X., Sheng, G., Li, H., Ren, X., Ma, J., Wang, J., Huang, Y., 2017.
Synthesis of few-layer graphene-like nanosheets from glucose: new facile approach
Macroscopic and spectroscopic insights into the mutual interaction of graphene
for graphene-like nanosheets large-scale production. J. Mater. Res. 31 (4), 455–467.
oxide, Cu(II), and Mg/Al layered double hydroxides. Chem. Eng. J. 313, 527–534.
Ali, R.M., Hamad, H.A., Hussein, M.M., Malash, G.F., 2016. Potential of using green
Hu, B., Ye, F., Ren, X., Zhao, D., Sheng, G., Li, H., Ma, J., Wang, X., Huang, Y., 2016. X-ray
adsorbent of heavy metal removal from aqueous solutions: adsorption kinetics, iso-
absorption fine structure study of enhanced sequestration of UIJVI) and SeIJIV) by
therm, thermodynamic, mechanism and economic analysis. Ecol. Eng. 91, 317–332.
montmorillonite decorated with zero-valent iron nanoparticles. Environ. Sci.: Nano
Bangash, F.K., Alam, S., 2009. Adsorption of acid blue 1 on activated carbon produced
2016 (3), 1460–1472.
from the wood of Ailanthus altissima. Braz. J. Chem. Eng. 26, 275–285.
Idris, M.N., Ahmad, Z.A., Ahmad, M.A., 2011. Adsorption equilibrium of malachite green
Bassyouni, D.G., Hamad, H.A., El-Ashtoukhy, E.-S.Z., Amin, N.K., El-Latif, M.M.A., 2017.
dye onto rubber seed coat based activated carbon. Int. J. Basic Appl. Sci. 11 (3),
Comparative performance of anodic oxidation and electrocoagulation as clean pro-
38–43.
cesses for electrocatalytic degradation of diazo dye Acid Brown 14 in aqueous
Jin, Z., Wang, X., Sun, Y., Ai, Y., Wang, X., 2015. Adsorption of 4-n-nonylphenol and
medium. J. Hazard. Mater. 335, 178–187.
bisphenol-A on magnetic reduced graphene oxides: a combined experimental and
Bazargan, A., McKay, G., 2012. A review e synthesis of carbon nanotubes from plastic
theoretical studies. Environ. Sci. Technol. 49 (15), 9168–9175.
wastes. Chem. Eng. J. 195–196, 377–391.
Kooh, M.R.R., Dahri, M.K., Lim, L.B.L., Lim, L.H., 2016. Batch adsorption studies on the
Box, G., Behnken, D.W., 1960. Some new three level designs for the study of quantitative
removal of acid blue 25 from aqueous solution using Azolla pinnata and soya bean
variables. Technometrics 2, 455–475.
waste. Arab J. Sci. Eng. 41, 2453–2464.
Chen, H., Zhao, J., Dai, G., 2011. Silkworm exuviae-A new non-conventional and low-cost
Kousha, M., Tavakoli, S., Daneshvar, E., Vazirzadeh, A., Bhatnagar, A., 2015. Central
adsorbentfor removal of methylene blue from aqueous solutions. J. Hazard. Mater.
composite design optimization of Acid Blue 25 dye biosorption using shrimp shell
186, 1320–1327.
biomass. J. Mol. Liq. 207, 266–273.
Ciardelli, G., Corsi, L., Marcucci, M., 2001. Membrane separation for wastewater reuse in
Kui, L., Xia, Z.G., Ke, W.X., 2012. A brief review of graphene-based material synthesis and
the textile industry. Conserv. Recycl. 31, 189–197.
its application in environmental pollution management. Chin. Sci. Bull. 57,
Deng, J., You, Y., Sahajwalla, V., Joshi, R.K., 2016. Transforming waste into carbon-based
1223–1234.
nanomaterials. Carbon 96, 105–115.
Lian, F., Xing, B., Zhu, L., 2011. Comparative study on composition, structure, and ad-
Dutt, K., Soni, R.K., 2013. A review on synthesis of value added products from poly-
sorption behavior of activated carbons derived from different synthetic waste poly-
ethylene terephthalate (PET) waste. Polym. Sci. Ser. B. 55, 430–452.
mers. J. Colloid Interface Sci. 360, 725–730.
El Essawy, N., Konsowa, A.H., Elnouby, M., Farag, H.A., 2016. A novel one step synthesis
Malard, L.M., Pimenta, M.A., Dresselhaus, G., Dresselhaus, M.S., 2009. Raman spectro-
for carbon based nanomaterials from polyethyleneterephthalate (PET) bottles. J. Air
scopy in graphene. Phys. Rep. 473, 51–87.
Waste Manag. Assoc. 1–13. http://dx.doi.org/10.1080/10962247.2016.1242517.
Mallakpour, S., Behranvand, V., 2016. Manufacture and characterization of nano-
Elkady, M.F., El-Sayed, E.M., Farag, H.A., Zaatout, A.A., 2014. Assessment of novel
composite materials obtained from incorporation of D-glucose functionalized
synthetized nanozirconium tungstovanadate as cation exchanger for lead ion de-
MWCNTs into the recycled poly(ethylene terephthalate). Des. Monomers Polym. 19,
contamination. J. Nanomater. 2014, 1–11.
283–289.
Elkady, M.F., Hassan, H.S., El-Sayed, E.M., 2015. Basic violet decolourization using al-
Mendoza-Carrasco, R., Cuerda-Correa, E.M., Alexandre-Franco, M.F., Fernandez-
ginate immobilized nanozirconium tungestovanadate matrix as cation exchanger. J.
Gonzalez, C., Gomez-Serrano, V., 2016. Preparation of high-quality activated carbon
Chem. 2015, 1–10.
from poly ethylene terephthalate (PET) bottle waste. Its use in the removal of pol-
Elkady, M., Shokry, H., Hamad, H., 2016. Effect of superparamagnetic nanoparticles on
lutants in aqueous solution. J. Environ. Manag. 181, 522–535.
the physicochemical properties of nano hydroxyapatite for groundwater treatment:
Mishra, S., Goje, A.Z., Zope, V.S., 2003. Chemical recycling, kinetics, and thermo-
adsorption mechanism of Fe(II) and Mn(II). RSC Adv. 6, 82244–82259.
dynamics of poly (ethylene terephthalate)(PET) waste powder by nitric acid hydro-
El-Remaily, M.A.A.A., Hamad, H.A., 2015. Synthesis and characterization of highly stable
lysis Polym. React. Eng. 11, 79–99.
superparamagnetic CoFe2O4 nanoparticles as a catalyst for novel synthesis of thiazolo
Nakagawa, K., Namba, A., Mukai, S.R., Tamon, H., Ariyadejwanich, P.,
[4,5-b]quinolin-9-one derivatives in aqueous medium. J. Mol. Catal. A: Chem. 404,
Tanthapanichakoon, W., 2004. Adsorption of phenol and reactive dye from aqueous
148–155.
solution on activated carbons derived from solid wastes. Water Res. 38, 1791–1798.
Fathy, M., Hamad, H., Kashyout, A., 2016. Influence of calcination temperatures on the
Nasuha, N., Hameed, B.H., 2011. Adsorption of methylene blue from aqueous solutio-
formation of anatase TiO2 nano rods with a polyol mediated solvothermal method.
nonto NaOH-modified rejected tea. J. Chem. Eng. 66, 783–786.
RSC Adv. 6, 7310–7316.
Ni, Z.H., Yu, T., Lu, Y.H., Wang, Y.Y., Feng, Y.P., Shen, Z.X., 2008. Uniaxial strain on
Forgacs, E., Cserh´ati, T., Oros, G., 2004. Removal of synthetic dyes from wastewaters: a
graphene: raman spectroscopy study and bandgap opening. ACS Nano 2, 2301–2305.
review. Environ. Int. 30, 953–971.
Parra, J., Ania, C., Arenillas, A., Rubiera, F., Palacios, J., Pis, J., 2004. Carbonaceous
Gao, J.J., Qin, Y.B., Zhou, T., Cao, D., Xu, P., Hochstetter, D., Wang, Y., 2013. Adsorption
materials from recycled PET [Materiales carbonosos obtenidos a partir del reciclado
of methylene blue onto activated carbon produced from tea (Camellia sinensis L.)
de PET]. Boletin De. la Soc. Esp. De. Ceram. Y. Vidr. 43, 547–549.
seed shells: kinetics, equilibrium, and thermodynamics studies. J. Zhejiang Univ.-Sci.
Pajootan, E., Arami, M., Rahimdokht, M., 2014. Application of carbon nanotubes coated
B (Biomed. Biotechnol.).
electrodes and immobilized TiO2 for dye degradation in a continuous photocatalytic-
Gopinath, K.P., Murugesan, S., Abraham, J., Muthukumar, K., 2009. Bacillus sp.mutant
electro-fenton process. Ind. Eng. Chem. Res. 53, 16261–16269.
for improved biodegradation of Congo red: random mutagenesis approach. Bioresour.
Rafatullah, M., Sulaiman, O., Hashim, R., Ahmad, A., 2010. Adsorption of methylene blue
Technol. 100, 6295–6300.
on low-cost adsorbents: a review. J. Hazard. Mater. 177, 70–80.
Hamad, H., Abd El-latif, M., Kashyout, A., Sadik, W., Feteha, M., 2014. Study on synthesis
Rahimdokht, M., Pajootan, E., Arami, M., 2016. Central composite methodology for
of superparamagnetic spinel cobalt ferrite nanoparticles as layered double hydroxides
methylene blue removal by Elaeagnus angustifolia as a novel biosorbent. J. Environ.
by co-precipitation method. Russ. J. Gen. Chem. 84, 2031–2036.
Chem. Eng. 4, 1407–1416.
Hamad, H.A., Abd El-latif, M.M., Kashyout, A.B., Sadik, W.A., Feteha, M.Y., 2015a.

67
N.A. El Essawy et al.
Saha, B., Ghoshal, A., 2005. Thermal degradation kinetics of poly(ethylene terephthalate)
from waste soft drinks bottles. Chem. Eng. J. 111, 39–43.
Sergiienko, R., Shibata, E., Kim, S., Kinota, T., Nakamura, T., 2009. Nanographite
structures formed during annealing of disordered carbon containing finely-dispersed
carbon nanocapsules with iron carbide cores. Carbon 47, 1056–1065.
Shen, Y., Lua, A.C., 2013. A facile method for the large-scale continuous synthesis of
graphene sheets using a novel catalyst. Sci. Rep. http://dx.doi.org/10.1038/
srep03037.
Sheng, G., Alsaedi, A., Shammakh, W., Monaquel, S., Sheng, J., Wang, X., Li, H., Huang,
Y., 2016a. Enhanced sequestration of selenite in water by nanoscale zero valent iron
immobilization on carbon nanotubes by a combined batch, XPS and XAFS in-
vestigation. Carbon 99, 123–130.
Sheng, G., Hu, J., Li, H., Li, J., Huang, Y., 2016b. Enhanced sequestration of Cr(VI) by
nanoscale zero-valent iron supported on layered double hydroxide by batch and XAFS
study. Chemosphere 148, 227–232.
Sheng, G., Tang, Y., Linghu, W., Wang, L., Li, J., Li, H., Wang, X., Huang, Y., 2016c.
Enhanced immobilization of ReO4- by nanoscale zerovalent iron supported on
layered double hydroxide via an advanced XAFS approach: implications for TcO4-
sequestration. Appl. Catal. B: Environ. 192, 268–276.
Sivakumar, P., Palanisamy, P.N., 2009. Adsorption studies of basic red 29 by anon-con-
ventional activated carbon prepared from Euphorbia antiquorum L. J. Chem.
Technol. Res. 1, 502–510.
Wang, H., Gao, H., Chen, M., Xu, X., Wang, X., Pan, C., Gao, J., 2016. Microwave-assisted
synthesis of reduced graphene oxide/titania nanocomposites as an adsorbent for
methylene blue adsorption. Appl. Surf. Sci. 360 (2016), 840–848.
Wu, Z.-L., Liu, Q., Chen, X.-Q., Yu, J.-G., 2015a. Preconcentration and analysis of
68
Ecotoxicology and Environmental Safety 145 (2017) 57–68
Rhodamine B in water and red wine samples by using magnesium hydroxide/carbon
nanotube composites as a solid-phase extractant. J. Sep. Sci. 38, 3404–3411.
Wu, Z.-L., Yang, H., Jiao, F.-P., Liu, Q., Chen, X.-Q., Yu, J.-G., 2015b. Carbon nano-
particles pillared multi-walled carbon nanotubes for adsorption of 1-naphthol: ther-
modynamics, kinetics and isotherms. Colloids Surf. A: Physicochem. Eng. Asp. 470,
149–160.
Yu, J.-G., Zhao, X.-H., Yang, H., Chen, X.-H., Yang, Q., Yu, L.-Y., Jiang, J.-H., Chen, X.-Q.,
2014. Aqueous adsorption and removal of organic contaminants by carbon nano-
tubes: review. Sci. Total Environ. 482–483, 241–251.
Yu, J.-G., Yu, L.-Y., Yang, H., Liu, Q., Chen, X.-H., Jiang, X.-Y., Chen, X.-Q., Jiao, F.-P.,
2015. Graphene nanosheets as novel adsorbents in adsorption, preconcentration and
removal of gases, organic compounds and metal ions. Sci. Total Environ. 502, 70–79.
Yu, L., Wu, X., Liu, Q., Liu, L., Jiang, X., Yu, J., Feng, C., Zhong, M., 2016a. Removal of
phenols from aqueous solutions by graphene oxide nanosheet suspensions. J.
Nanosci. Nanotechnol. 16, 12426–12432.
Yu, J.-G., Yue, B.-Y., Wu, X.-W., Liu, Q., Jiang, X.-Y., Zhong, M., Li, H.-Y., Li, S.-S., Chen,
X.-Q., 2016b. The covalently organic functionalization of graphene: methodologies
and protocols. Curr. Org. Chem. 20, 1284–1298.
Yuan, Y., Cabasso, I., Liu, H., 2008. Surface morphology of nanostructured polymer-based
activated carbons. J. Phys. Chem. B 112, 14364–14372.
Zhang, J., Wang, X., Qi, G., Li, B., Song, Z., Jiang, H., Zhang, X., Qiao, J., 2016. A novel N-
doped porous carbon microsphere composed of hollow carbon nanospheres. Carbon
96, 864–870.
Zhao, H., Qiu, F., Yan, J., Wang, J., Li, X., Yang, D., 2016. Preparation of economical and
environmentally friendly graphene/palygorskite/TiO2 composites and its application
for the removal of methylene blue. Appl. Clay Sci. 121–123, 137–145.